US2541384A - Method of making a luminescent zinc sulfide - Google Patents
Method of making a luminescent zinc sulfide Download PDFInfo
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- US2541384A US2541384A US790242A US79024247A US2541384A US 2541384 A US2541384 A US 2541384A US 790242 A US790242 A US 790242A US 79024247 A US79024247 A US 79024247A US 2541384 A US2541384 A US 2541384A
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- zinc
- zinc sulphide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/611—Chalcogenides
- C09K11/612—Chalcogenides with zinc or cadmium
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- Theinvention relates to a method for the production of a luminescent copper activated zinc sulphide comprising the adjustment of the position of the green band in the spectrum of said zinc sulphide and of the relative intensities of the green emission to the blue emission by varyingthe amounts of free elemental sulphur or free metallic zinc present in the zinc sulphide before firing the same in an inert atmosphere and by adding different types of halide compounds according to whichever colour is desired.
- the water adhering from the washing can be removed by heating the powder again, preferably in vacuum.
- Presence of free sulphur in the zinc sulphide *before firing tends to shift the peak of the green band to the blue part of the spectrum, while presence of metallic zinc moves the peak to the yellow part of the spectrum.
- the quantity of sulphur or zinc added should be suflicient to produce an atmosphere saturated with sulphur or pends entirely on the prevailing condtions, fo example size of the muffle, shape of the crucible, tight fit of the crucible lid, the rate of heating and so on. Generally it has been observed that, with a material well enclosed in a crucible, about 5% sulphur or 5% zinc metal are sufficient to produce the maximum shifting. If a material has to be prepared which shows only the green band Without, or with only a Weakly developed, blue band an inert atmosphere, for example nitrogen, should be used.
- halide compounds added to the zinc sulphide before the firing is also of influence on the position of the green band and on the development of the blue band.
- Alkalihalides are favourable for a greenish shade, and earth-alkalihalides for the yellow green.
- Magnesium chloride increases the intensity of the blue band and diminishes the intensity of the green emulsion.
- a material with a predominant blue emission isobtained by adding about 10% magnesium chloride.
- the position of the green band depends again on the presence of free sulphur or zinc and one of these elements is added accordving to whichever shade of colour is desired.
- the materials prepared according to the in:- vention are excited to luminescence by light, cathode rays or by the radiation of radioactive substances. It is accordingly possible toprepare 3 for instance a bluish luminescent radioactive substance with a bluish luminescent zinc sulphide prepared as described above.
- the final product has the sphalerite structure and the smaller remaining part has. thewurtzite structure.
- pure zinc sulphide is first heated together with pure sulphur up to 400 C. in-a hydrogen atmosphere.
- the finished materiali shows a green luminescencewith a peak at 520m
- Pure xinc sulphide issprepared :and' analysesd.
- Sulphur compounds like. zinc thiosulphate; are;re.- moved by washing with;.sodium' carbonate. S0111?- tion.
- Zinc oxide aisextracted asdescribedzin-Exaamplev 1 andthamaterial carefnlly dried. .zThe 'sulphideris then..-mixedwith.about 5% zinc. dust,
- the product has azshort.-afterglow only.
- a process. for the production of a luminescent 'zinc sulphide comprising the steps of amixing zinc sulphide, a copper activator, a halideselectad from the group ,consistingof the alkali metals and alkalineeearth 'metals, .and. less than about 15%,,o-f;one of the, elements constituting pure zinc sulphide, andheatingithe-so formed mixture to .the reaction temperatureethereof inan inert.at-
- a process for theproiductionofta luminescent zinc sulphide comprising-the-stepsotcmixingtzinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to the reaction temperature thereof in a nitrogen atmosphere.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C. to about 1200 C. in an atmosphere of said element of pure zinc sulphide in volatile form.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, a. halide selected from the roup consisting of alkali metals and alkaline-earth metals, and less than about 5% of metallic zinc, and heating the so formed mixture to a temperature of about 1200 C. in an inert atmosphere.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of sulphur, and heating the so formed mixture to a temperature of about 1200 C. in an inert atmosphere.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of metallic zinc, and heating the so formed mixture to a temperature of about 1200 C. in an atmosphere of volatile zinc.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of sulphur, and heating the so formed mixture to a temperature of about 1100 C. in an atmosphere of volatile sulphur.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C. to about 1200 C. in an inert atmosphere.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, an alkali halide, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C, to about 1200 C. in a nitrogen atmosphere.
- a process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, an alkaliearth halide, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C. to about 1200 C. in a nitrogen atmosphere.
- a process for the production of a luminescent zinc sulphide comprising the steps of precipitating zinc sulphide from a solution of a zinc salt, washing the so formed precipitated material with dilute acetic acid, washing the so acidified material with distilled water, drying the so washed material; mixing the so dried material with approximately 5% of sulphur by weight, approximately 2% of sodium chloride by weight, approximately 0.1% of copper chloride by weight, and heating the so formed mixture at approximately 1100 C. in an atmosphere of nitrogen.
- a process for the production of a luminescent zinc sulphide comprisin the steps of precipitating zinc sulphide from a solution of a zinc salt, washing the so formed precipitated mate-' rial with sodium carbonate solution, washing the so treated material with dilute acetic acid, washing the so acidified material with distilled water, drying the so washed material, mixing the so dried material with approximately 5% of zinc dust by weight, 5% of barium chloride by weight, 1% of sodium chloride by weight, 0.1% of copper chloride by weight, and heating the so formed mixture at about 1200 C. in an atmosphere of nitrogen.
- a process for the production of a luminescent zinc sulphide comprising the steps of precipitating zinc sulphide from a solution of a zinc salt, washing the so formed precipitated material with sodium carbonate solution washing the so treated material with dilute acetic acid, washing the so acidified material with distilled water, dryin the so washed material, mixing the so dried material with approximately 10% magnesium chloride by weight, approximately 5% of zinc dust by weight, approximately 0.1% of copper chloride by weight and heating the so formed mixture at'approximately 1200 C. in an atmos phere of nitrogen.
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Description
Patented Feb. 13, 1951 METHOD OF MAKING A LUMINESCENT ZINC SULFIDE Siegfried Rothschild, London, England, assignor to The Hartford National Bank and Trust Company, Hartford, Conn., as trustee No Drawing. Application December 6, 1947, Se-
rial No. 790,242. In Great Britain July 29, 1941 Section 1, Public Law 690, August 8, 1946 Patent expires July 29, 1961 Among the different luminescent substances zinc sulphide activated with copper is still one of the most important. The spectrum of the luminescence of this material always shows a green 13 Claims. (Cl. 252301.6)
band and in addition a blue band has often been I observed. The figures given for the spectral position of the green band vary from 515 to 550 m the peak of the blue band has usually been observed at about 460 m Theinvention relates to a method for the production of a luminescent copper activated zinc sulphide comprising the adjustment of the position of the green band in the spectrum of said zinc sulphide and of the relative intensities of the green emission to the blue emission by varyingthe amounts of free elemental sulphur or free metallic zinc present in the zinc sulphide before firing the same in an inert atmosphere and by adding different types of halide compounds according to whichever colour is desired.
As raw material for the production of zinc sulphide solutions of zinc salts are treated usually with hydrogen sulphide. The precipitate thus obtained is of a rather composite nature. It consists, not only of a more or less hydrated zinc sulphide, but free sulphur may also be present or sulphur compounds like thiosulphates. The material may furthermore contain in adsorption salts from the mother liquor. The presence of any of these substances in the precipitated zinc sulphide proved to be of a definite influence on the luminescent properties of the finished material. The same applies of course to zinc sulphide prepared by any other method than precipitation with hydrogen sulphide. The exact composition of the zinc sulphide has therefore to be ascertained, before it is used for the preparation of the luminescent material. Adsorbed salts and zinc oxide can be removed by washing with diluted acetic acid and subsequently with distilled water.
The water adhering from the washing can be removed by heating the powder again, preferably in vacuum.
Presence of free sulphur in the zinc sulphide *before firing tends to shift the peak of the green band to the blue part of the spectrum, while presence of metallic zinc moves the peak to the yellow part of the spectrum. The quantity of sulphur or zinc added should be suflicient to produce an atmosphere saturated with sulphur or pends entirely on the prevailing condtions, fo example size of the muffle, shape of the crucible, tight fit of the crucible lid, the rate of heating and so on. Generally it has been observed that, with a material well enclosed in a crucible, about 5% sulphur or 5% zinc metal are sufficient to produce the maximum shifting. If a material has to be prepared which shows only the green band Without, or with only a Weakly developed, blue band an inert atmosphere, for example nitrogen, should be used.
The type of halide compounds added to the zinc sulphide before the firing is also of influence on the position of the green band and on the development of the blue band. Alkalihalides are favourable for a greenish shade, and earth-alkalihalides for the yellow green. Magnesium chloride increases the intensity of the blue band and diminishes the intensity of the green emulsion.
A material with a predominant blue emission isobtained by adding about 10% magnesium chloride. The position of the green band depends again on the presence of free sulphur or zinc and one of these elements is added accordving to whichever shade of colour is desired.
It has to be assumed that these reactions are affected by the presence of an excess of either zinc or sulphur with the result that the finished crystallized material contains lattice disturbances of a different character depending on the addition of sulphur or zinc. It is further plausible from the formulas given above that the kind of halide salts used influences the luminescence. According to the modern theories about luminescence the existence of lattice defects produces. new energy levels in the crystal structure. Light will be emitted by a jump of an electron into one of these additional levels. The wave length .of the emitted light will depend on the differences in energy between these levels which accounts for the different positions of the peak of the green bandin the spectrum and the appearance of a blue band.
The materials prepared according to the in:- vention are excited to luminescence by light, cathode rays or by the radiation of radioactive substances. It is accordingly possible toprepare 3 for instance a bluish luminescent radioactive substance with a bluish luminescent zinc sulphide prepared as described above.
In British specification No. 473,715 a'method of preparing a'layer of phosphorescent material has been described by heating pure zinc sulphide together with a flux to a temperature below the softening point of glass and for a time. not aex.-- ceeding half an hour, so that the greater partsof.
the final product has the sphalerite structure and the smaller remaining part has. thewurtzite structure. In the example given in said specification pure zinc sulphide is first heated together with pure sulphur up to 400 C. in-a hydrogen atmosphere.
for minutes to about 400 C. During the second heating no speciaLmeasures againstoxid-ation are taken and air is therefore admitted. wurtzite/sphalerite ratiois of importance for the: decay timeo'f the material after irradiation, a high Wurtzitecontent producesa-long persistent afterglow-while a hi'gh'sphal'erite content contributes to a short' afterglow. The posifiring, whichprovides the material with luminescent properties.
' It is however an ;essential:feature of the. pres ent. invention, that duringthe firing process, which causes the zincsulphide to luminesce,cop-
per compounds as Welles halide compounds are" "present simultaneously with elemental sulphur Theeifect of I .or zinc in an inert atmosphere. .the. sulphur or zinc onthe "spectral'p'osition of the copper band does not take placegwhenthe zinc sulphide is first heated with sulphuror zinc only and thenafterwards heated again with copper and halide compoundsbutwithout an addition of sulphur or zinc. The dissociation reac- 11110115, describedv above, which also affectthe copuner. compounds are influenced bythe presence iofielemental sulphur or zinc,-and itis therefore not possible to produce the. sameaeifect: by-a heating process intwo; stages.
:Furthermore any reheating .of the'copper activated zinc sulphide with.-admission-.of air.-.-af fects' the spectral distribution of the .ll-uminescence although it may not: appreciably: alter the =wurtzite/sphalerite ratio. It has also to be npointed out that, when the: heating of the .zinc
:sulphide with sulphur as described-in British :specification No. 473,715 is carried out in a :hydrogen atmosphere, a reaction betweensulphur "andhydrogen takes place with-formation of-hydrogen sulphide. TheLpresence of'ihydrogen sulphide has however .anzefiect 'on thesspectrum of the luminescence of the zinc..sulph-ide=completely different: from the efiect ofxelemental'sul- .phur as used in.thepresentinvention; But: also this efieot of I hydrogensulphideon the luminescence is only noticeable, whenthefiring. isicarr-ied This zinc sulphide, which substantially consists of cubic sphalerite is caused to;,1umines,ce by heating it again together with a fluxas. K61:
4 out in presence of the copper and halide com pounds and not without these substances.
In said specification it is further stated that instead of alkali. halides other halide: compounds may be used which exert differentinfiuences on ..the durability of the phosphorescence of the material during operation. No reference is however madeconcerning the influence of such compounds on the spectral emission.
.111 Britishspecification No. 492,923 a process for producing a zinc sulphide composition that re- .mainsphosphorescent for a lengthy period has been described characterized in that a content of'zinc oxide'in theend product amounting to '-about'2% is-obtaine'd. The material prepared according to the present invention does not contain anysuchamounts of zinc oxide after firing, on the contrary zinc oxide eventually present before the'fi'ring is removed and care has to be taken that no zinc oxide is formed while the firing is carried out.
The following nonelimitative examples Lillusatrate the preparation :of luminescent Zino;sn1.-.- phi'des according to the presentainvention.
Erzta'mplev 1' Pure zincsulphide is; preparedby. precipitationof a; purified; zinc;solution. Therwashed and dried sulphide is washed with diluted acetic acid, subsequently with distilled Water, until itiiS freefrom chloridesand any. zinc salts. :The sulphide is then *dried preferably. in vacuum and afterwards well: mh ed'-with;about.5.=% 2% NaCl and-0.1% CuC1210n l1 kgnmaterial. The mixture is filledinxcrucibles with a well fittin lid and. heated up in 2 hours inan atmosphere of nitrogen to about 1100 Q, .then. kept at this temperature-for one hour: in.an atmospherezof nitrogen. The finished materialishows a green luminescencewith a peak at 520m Example? Pure xinc sulphide issprepared :and'analysed. Sulphur compounds like. zinc thiosulphate; are;re.- moved by washing with;.sodium' carbonate. S0111?- tion. Zinc oxideaisextracted asdescribedzin-Exaamplev 1 andthamaterial carefnlly dried. .zThe 'sulphideris then..-mixedwith.about 5% zinc. dust,
15 Bach and .l1%.NaC1, activated withcopper ffi'lled in crnciblesawith wellifitting lids,,. grad; .ually heated up,to.:about;12(l0 cChandv kept; at. this temperaimre; inoan atmosphere. ofxnitrogen; for? v1 hour. '.Thefinishedproduct, shows a yellowgreenaluminescencez-with a;.peak at- 545 m Example. 3'
Zincysulphide prepared and treatedtas..de. scribed. in Example 2 but; instead ofv BaGlz and NaCl 10% 'MgClz crystallized: is used.
The. material shows a blue fluorescence with =a. preponderance of the. blue band. the green band -.is-;on;ly weakly developed.
The product has azshort.-afterglow only.
'I' claim:
1. A process. for the production of a luminescent 'zinc sulphide, comprising the steps of amixing zinc sulphide, a copper activator, a halideselectad from the group ,consistingof the alkali metals and alkalineeearth 'metals, .and. less than about 15%,,o-f;one of the, elements constituting pure zinc sulphide, andheatingithe-so formed mixture to .the reaction temperatureethereof inan inert.at-
mosphere.
. 2. A process for theproiductionofta luminescent zinc sulphide, comprising-the-stepsotcmixingtzinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to the reaction temperature thereof in a nitrogen atmosphere.
3. A process for the production of a luminescent zinc sulphide, comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C. to about 1200 C. in an atmosphere of said element of pure zinc sulphide in volatile form.
4. A process for the production of a luminescent zinc sulphide, comprising the steps of mixing zinc sulphide, a copper activator, a. halide selected from the roup consisting of alkali metals and alkaline-earth metals, and less than about 5% of metallic zinc, and heating the so formed mixture to a temperature of about 1200 C. in an inert atmosphere.
5. A process for the production of a luminescent zinc sulphide, comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of sulphur, and heating the so formed mixture to a temperature of about 1200 C. in an inert atmosphere.
6. A process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of metallic zinc, and heating the so formed mixture to a temperature of about 1200 C. in an atmosphere of volatile zinc.
'7. A process for the production of a luminescent zinc sulphide, comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of sulphur, and heating the so formed mixture to a temperature of about 1100 C. in an atmosphere of volatile sulphur.
8. A process for the production of a luminescent zinc sulphide, comprising the steps of mixing zinc sulphide, a copper activator, a halide selected from the group consisting of the alkali metals and alkaline-earth metals, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C. to about 1200 C. in an inert atmosphere.
9. A process for the production of a luminescent zinc sulphide, comprising the steps of mixing zinc sulphide, a copper activator, an alkali halide, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C, to about 1200 C. in a nitrogen atmosphere.
10. A process for the production of a luminescent zinc sulphide comprising the steps of mixing zinc sulphide, a copper activator, an alkaliearth halide, and less than about 5% of one of the elements constituting pure zinc sulphide, and heating the so formed mixture to a temperature of about 1100 C. to about 1200 C. in a nitrogen atmosphere.
11. A process for the production of a luminescent zinc sulphide comprising the steps of precipitating zinc sulphide from a solution of a zinc salt, washing the so formed precipitated material with dilute acetic acid, washing the so acidified material with distilled water, drying the so washed material; mixing the so dried material with approximately 5% of sulphur by weight, approximately 2% of sodium chloride by weight, approximately 0.1% of copper chloride by weight, and heating the so formed mixture at approximately 1100 C. in an atmosphere of nitrogen.
12. A process for the production of a luminescent zinc sulphide comprisin the steps of precipitating zinc sulphide from a solution of a zinc salt, washing the so formed precipitated mate-' rial with sodium carbonate solution, washing the so treated material with dilute acetic acid, washing the so acidified material with distilled water, drying the so washed material, mixing the so dried material with approximately 5% of zinc dust by weight, 5% of barium chloride by weight, 1% of sodium chloride by weight, 0.1% of copper chloride by weight, and heating the so formed mixture at about 1200 C. in an atmosphere of nitrogen.
13. A process for the production of a luminescent zinc sulphide comprising the steps of precipitating zinc sulphide from a solution of a zinc salt, washing the so formed precipitated material with sodium carbonate solution washing the so treated material with dilute acetic acid, washing the so acidified material with distilled water, dryin the so washed material, mixing the so dried material with approximately 10% magnesium chloride by weight, approximately 5% of zinc dust by weight, approximately 0.1% of copper chloride by weight and heating the so formed mixture at'approximately 1200 C. in an atmos phere of nitrogen.
SIEGFRIED ROTHSCHILD.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,352,035 Strubig June 20, 1944 FOREIGN PATENTS Number Country Date 473,715 Great Britain Oct. 19, 1937 492,923 Great Britain Sept. 29, 1938
Claims (1)
1. A PROCESS FOR THE PRODUCTION OF A LUMINESCENT ZINC SULPHIDE, COMPRISING THE STEPS OF MIXING ZINC SULPHIDE, A COPPER ACTIVATOR, A HALIDE SELECTED FROM THE GROUP CONSISTING OF THE ALKALI METALS AND ALKALINE-EARTH METALS, AND LESS THAN ABOUT 5% OF ONE OF THE ELEMENTS CONSTITUTING PURE ZINC SULPHIDE, AND HEATING THE SO FORMED MIXTURE TO THE REACTION TEMPERATURE THEREOF IN AN INERT ATMOSPHERE.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2728731A (en) * | 1952-09-09 | 1955-12-27 | Sylvania Electric Prod | Method of making electroluminescent phosphors |
US2755255A (en) * | 1953-01-30 | 1956-07-17 | Gen Electric | Electroluminescent zinc sulfide phosphor |
US2874128A (en) * | 1956-12-24 | 1959-02-17 | Westinghouse Electric Corp | Phosphor |
US2951813A (en) * | 1956-12-24 | 1960-09-06 | Westinghouse Electric Corp | Method of preparing an electroluminescent zinc sulfide phosphor |
US2965580A (en) * | 1957-07-18 | 1960-12-20 | Du Pont | Treating processes for improving physical properties of phosphors |
US3043781A (en) * | 1958-06-30 | 1962-07-10 | Sylvania Electric Prod | Barium silicate phosphor |
US20050224760A1 (en) * | 2002-07-12 | 2005-10-13 | Chao-Nan Xu | Highly bright mechanoluminescence material and process for producing the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB473715A (en) * | 1935-07-30 | 1937-10-19 | Philips Nv | Improved method of preparing phosphorescent material |
GB492923A (en) * | 1937-09-13 | 1938-09-29 | J D Riedel E De Haeen Ag | An improved process for producing a phosphorescent zinc sulphide composition |
US2352035A (en) * | 1944-06-20 | Luminescent material |
-
1947
- 1947-12-06 US US790242A patent/US2541384A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2352035A (en) * | 1944-06-20 | Luminescent material | ||
GB473715A (en) * | 1935-07-30 | 1937-10-19 | Philips Nv | Improved method of preparing phosphorescent material |
GB492923A (en) * | 1937-09-13 | 1938-09-29 | J D Riedel E De Haeen Ag | An improved process for producing a phosphorescent zinc sulphide composition |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2728731A (en) * | 1952-09-09 | 1955-12-27 | Sylvania Electric Prod | Method of making electroluminescent phosphors |
US2755255A (en) * | 1953-01-30 | 1956-07-17 | Gen Electric | Electroluminescent zinc sulfide phosphor |
US2874128A (en) * | 1956-12-24 | 1959-02-17 | Westinghouse Electric Corp | Phosphor |
US2951813A (en) * | 1956-12-24 | 1960-09-06 | Westinghouse Electric Corp | Method of preparing an electroluminescent zinc sulfide phosphor |
US2965580A (en) * | 1957-07-18 | 1960-12-20 | Du Pont | Treating processes for improving physical properties of phosphors |
US3043781A (en) * | 1958-06-30 | 1962-07-10 | Sylvania Electric Prod | Barium silicate phosphor |
US20050224760A1 (en) * | 2002-07-12 | 2005-10-13 | Chao-Nan Xu | Highly bright mechanoluminescence material and process for producing the same |
US7297295B2 (en) * | 2002-07-12 | 2007-11-20 | Japan Science And Technology Agency | Highly bright mechanoluminescence material and process for producing the same |
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